Process of producing crystallized metallic lead plates



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C. PAYEN. PROCESS 0E PRODUGING GEYSTALLIZED METALLIC LEAD PLATES. No. 440,268. Patented Nov. 11, 1890.

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EEUGESS 0E PEODUGING GEYSTALLIZED METALLIC LEAD PLATES. No. 440,268. Pgtented Nov. 11, 1890.

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i UNITED STATES ATENT OFFICE.

CLMENT PAYEN, OF PHILADELPHIA, PENNSYLVANIA, ASSIGNOR TO THE ELECTRIC STORAGE BATTERY COMPANY, OF GLOUCESTER CITY, NEIV JERSE Y.

PROCESS F PRODUCING CRYSTALLIZED METALLIC LEAD PLATES.

SPECIFICATION forming part of Letters Patent No. 440,268, dated November 11, 1890.

Application iled January 16, 1888. Serial No. 260,900. (No specimens.)

To all whom t may concern.-

Be it known that. I, CLMENT PAYEN, a citizen of the Republic of France, but now residing at the city of Philadelphia, in the county 0f Philadelphia and State of Pennsylvania, have invented a certain new and Improved Process of Producing Crystallized Metallic Lead Plates, of which the following` is a specification.

io My invention relates to a method of producing porous crystallized metal lead plates for use as the elements of a secondary or storage battery.

The invention consists in fusing with chloride of lead the chlorides of zinc and cadmium or metallic zinc and chloride of cadmium therewith, and which are added either before or during the fusing of the chloride of lead, then discharging the liquid or molten mass zo into a mold, and in cooling assuming a crystallized form, and then reducing the cast plate or other structure to ametallic state, whereby a strong porous crystallized structure will be produced especially adapted for use as an 2 5 element of a secondary or storage battery.

In the accompanying drawings I have illustrated a plant and suitable apparatus for the conduct of my method of producing crystallized lead plates, and in such forms, respectively, as I have found practically etlicient, in which- Figure lis a vertical central section through a melting or fusing furnace of my improved construction, showing the crueible pivotally 3 5 supported therein and operated by a lever for discharging the contents thereof. Fig. 2 is a top or plan view of my improved mold made in two sections and hinged to each other, and showing, also, the means for clamping the two sections together. Fig. 3 is an end view of my improved mold constructed in two scctions and the means for clamping the same together. Fig. 4 is a perspective view of my improved mold made in two sections hinged to each other and showing, also, the interior formation of the two sections thereof. Fig. 5 is a perspective View of the bivalved mold for framing the crystallized metallic plates. Fig. 6 is an end view of the two sections of 5o the framing-mold clamped together. Fig. 7

is a top or plan view of said framing-mold, showing, also, the clamping device; and Figs.

8 and 9 are diagrammatic views showing the first and second electrolytic actions to which the crystallized plates are subjected in order to bring each of them to a metallic state.

Referring to the accompanying drawings,

A is the furnace, constructed of brick or other suitable material and of any suitable form.

B is the grate located and supported in the 6o lower part of the furnace, access to the grate B for firing the furnace or for any other purpose being had by means of a door b. Beneath the grate B is an ash-pit C, closed from the outside by a door c.

D is the draft-flue leading to the chimney D.

E is an arch, made of brick or other refractory material, in the upper part of the furnace, which is supported in position on a metallic annular plate @,with a central opening therein. 7o The annular plate e is held in position by means of columns f, arranged and supported in the brick-work of the furnace in any suitable manner.

F is a porcelain crueible or melting-pot, open at the top, around the outer circumference of which is formed a layer d of amianthus, asbestus, or other suitable material, and between this layer d and the lnetallic pot F is a film or layerof sand f of any desired thick- 8o ness. This metallic capsule or pot F is pivotally supported in a central position within the furnace and is operated from the outside by a lever f2, attached to one of the journals of the metallic pot, whereby the crueible F 8 5 may be readily tilted for discharging the contents into a receptacle or mold for further treatment.

II is an inclined metallic hopper, provided with a removable stopper 7L, arranged so as to 9o permit of the charging of the salts of the metal or other material into the crueible F for the melting ofthe same after the furnace has been fired.

I is a sliding door, operated in any suitable manner to allow of the discharge of the liquid or molten mass or compound into a suitable mold for causing the same to assume a crystallized form.

Having described and pointe-d out the char- 10o acteristic features of the melting or fusing furnace, I Will now proceed to describe the iirst step in the process for the production of a crystallized metallic lead plate of a given size, say from six to eight inches square.

I take for the base of the charge chloride of lead, and to which I add two per cent., by weight, (more or less,) of chloride of cadmium and two percent., by weight, (more or less,) of chloride of zinc, or of metallic zinc, and these chlorides namely-the chloride of cadmium and chloride of zinc-or metallic zinc may be added either before or during fusion in any preferred suitable or desirable manner; butI prefer to add the chloride of cadmium or chloride of zinc, or both, gradually during the fusion of the chloride of lead in the crucible F. The proportion of chloride of cadmium and of chloride of zinc, or of metallic zinc, to the charge of chloride of lead will in each case depend upon the degree of porosity desired in the finished plate. It will therefore be understood that by simply varying the proportions of the chlorides, or of the metallic zinc, mixed with the charge of chloride of lead` any degree of porosity required maybe readily obtained. l have found by experience that when the aforesaid chloride of cadmium and chloride of zinc or metallic zinc are added to the charge of chloride of lead, the plates thereby formed after fusion and crystallization possess great strength, and that the fractures thereof offer a clean, bright, and uniform surface,or, in other words, the plate is much stronger than it would be if the chloride of cadmium had not formed an element of the compound for treatment in the production of such plate. ever, obtained good results by the substitution of an ammoniacal salt for the chloride of cadmium. The simple addition of the chloride of cadmium to the lead chloride enables me to obtain a crystallized plate which is not hygroscopic, and this is a very necessary condition, especially when it is desired to form a lead frame around the plate for the purpose of obtaining a good contact by electrolytic action. I have found that when metallic zinc or chloride of zinc alone has been added to the charge of chloride of lead the plate after crystallization has taken place Will be more or less hygroscopic, yet not to an extent to impair the ultimate utility of the plate after reduction to a metallic state, especially if no great degree of porosity is desired, While on the other hand if the chloride of cadmium, which of itself is not of a deliquescent nature, be added to the mass or compound excellent results can be readily obtained.

In the production of crystallized plates for electrical accumulators or storage-battery systems or other analogous uses I prefer to use the chloride of cadmium in conjunction with chloride of zincor metallic zinc in the charge of chloride of lead in excess for the production of such crytallized plates, because they will possess greater strength as well as a greater degree of porosity. After the charge I have, howhas reached a liquid state therein` the crucible is then tilted by means of the leverf2 and the sliding door I at the same time raised sufliciently to permit ofthe discharge of the molten or liquid mass or compound into the mold M through the mouth m thereof.

The selection of material for the mold M is of some considerable importance, and the character of the interior surface of the mold is likewise important and should be perfectly smooth. I have found that the best mold is that made of either brass or bronze. Molds made of malleable iron or cast-iron become deteriorated in a short time by use, while in the use of those made of iron the chloride of lead is apt to adhere to the sides thereof. The same objection has been found to exist with the use of porcelain molds. Those made of lead require the exercise of care in use, 0W- ing to the tendency of the metal to melt, yet, nevertheless, good results may be obtained by the use of lead ones with care in thehandling of them. The mold to which I give preference is one made of either brass or bronze and composed of two symmetrical sections m and m2, chamfered, as shown, for instance, in Fig. 4, and the two sections united to each other by means of hinges m3 and held togetherby means of catches or pawls'm, secured to the extremities of the shaft m5, held in bearings m7, formed with one of the sections and operated by a lever m4, as shown, for instance, in Figs. 2 and 3. The two sections forming the crystallizing-mold M may be formed so that each will be of a uniform thickness of metal and the thickness of each section varying from two to tive millimeters, according to the dimensions of the crystallized metallic plates to be formed. This similarity and uniform thickness of each section is for some purposes advantageous,for the reason that crystallization therein commences from each side of the mold, and therefore if the two sections are of equal thickness the cooling-point of each will be attained at the same time and the crystals formed in the mass will meet in the middle, and thus the line of cleavage of the crystals will be the same throughout the entire crystallized plate in parallel columns.

I have found that while it is preferable to have the two sections of the mold of equal thickness, yet at the same time it is not absolutely necessary; but when they are not of equal thickness of metal the cooling off of the material discharged into the same will be unequal, and as a consequence the line of meeting of the columns of crystals willbe more to one side of the mold than to the other, which may be advantageous in some instances.

When the molten or liquid mass or compound from the Crucible F has been discharged into the casting-mold M, in a few minutes thereafter solidiflcation will take place in the IOC IIO

cooling off of the same therein and the plate cast or formed will become crystallized. In some instances it may be well to heat the mold M previous to charging the molten or liquid mass or compound into the same, say, to a temperature of 150 centigrade, (more or less,) and still obtain good results in the crystallization of the plate. When the plate crystallized has become solid to a greater or less degree, the sections are unclamped and the plate then removed into a framing-mold N for casting around the crystallized plate a frame of lead or other suitable material.

The bivalved framing-mold N consists of two sections n and n', made of cast-iron or other suitable material. The section n of the framing-mold N has an upper flange n2 around the sides thereof when in the form of a rectangular parallelopipedon and with a beveled tlange or rim n3, formed on the four interior sides of the bottom. Wth the section n is formed a funnel-shaped trough or neck n4 for the introduction of material into the mold, when the two sections n and n are clamped together by means of the pawls or catches a5 and n, rigidly secured to each end of the shaft 117, held in bearings ns and a9, secured to the exterior surface of the section n', and operated by a lever n10, which causes the pawls or catches a5 and a6 to engage with the strengthening-strip nu, formed with or secured to the exterior surface of the opposite section. The section n has an interiorbeveled rim n.12, corresponding with the beveled rim n3 of the section n. The four sides or edges of the section n are slightly deected downward, and a series of niches or semicircular grooves w13 are formed in the under edges, forming air-holes when the two sections are clamped together. In the section n', as shown in Fig. 7, two or more openings n are formed at suitable distances apart for the introduction of small pins for holding the crystallized plate in proper position in the mold to allow lead or other suitable material to become cast around the platein the form, preferably, of a beveled frame, with a tongue or support n.15, for a purpose to be presently described.

The manner of castinga frame around the crystallized plate will now be explained.

The crystallized plate is removed from the mold M to the framing or casting mold N and placed in the center thereof, so that the beveled rim of the mold will be in close proximity to the four sides of the rectangular-shaped plate, and in this form the section n of the mold is laid upon the same so as to occupy the position shown in Fig. 7, and the two sections clamped together by means of the lever n10, operated in the manner hereinbefore fully explained, pins being inserted through the small openings 11.14 in the section n in order to hold the crystallized plate firmly in position. The mold is then elevated and the liquid or molten lead poured into the mold through the funnel-shaped trough n4, and the same passing around the crystallized plate held therein and in cooling off becoming solidly affixed to or cast around the four sides of the crystallized plate in the form of a beveled frame or border. When the frame cast around the crystallized plate has become perfectly solid, the plate may then be removed from the mold for reduction to a metallic state. A series of crystallized chloride plates treated in the manner hereinbefore described may thenbe placed in a glass canister or other receptacle G, containing water and ten per cent. (more orless) otsulphuric acid, the crystallized plates 2 being immersed in the solution in the glass canister G and alternated with plates of equal dimensions of ordinary lead or artificial charcoal 3, each having a tongue Qc, all the crystallized plates 2 being` connected through their tongues or supports w15 with a wire 4, while the lead or charcoal plates 3 are connected through their tongueswith a Wire 5, and the two systems of plates insulated from each other by means of the insulating-rods r, made of rubber or other suitable material, and from the canister G by means of the glass insulators r', mounted on the horizontal bars r2, made of rubber or other suitable insulating material in the bottom of the glass canister G, as shown, for instance, in Fig. 8, the system of crystallized plates being connected with the negative electrode s ot the dynamo S, while the system of lead or charcoal plates is connected with the positive electrode n of the dynamo S, and in consequence of the electrolytic action which takes place the oxygen and chlorine will be separated and caused to attack the system of lead or charcoal plates, while on the system of crystallized plates there will remain zinc and cadmium metallic. The crystallized plates thus treated are then removed and immersed in another glass canister or receptacle G', containing water and sulphuric acid in about the same proportions as hereinbefore mentioned. In this second receptacle G the crystallized plates are again alternated with others of ordinary lead or artificial charcoal, as in the previous instance, and the two systems of plates, insulated, respectively, from each other and the glass canister G', are again united by two separate wires 6 and 7, connected with a dynamo S', as in the rst instance described, with this exception, that the negative electrode s is connected with the system of lead or charcoal plates through the tongues x, while the positive electrode 'm17 is connected with the system of crystallized plates through the tongue p15, as shown in Fig. 9. By this second electrolytic action which takes place the zinc cadmium and hydrogen metallic are deposited on the lead or IOO IIO

charcoal plates and the oxygen caused to atmetallic lead plates produced by this method of treatment with the desired degree ot' porosity will have as well great consistencyand rigidity and maybe made of anydesired form or dimensions.

In my applications for Letters Patent, Serial No. 245,378, of July 26, 1887; Serial No. 261,953, of January 26, 1888; Serial No. 266,949, of March l2, 1888, and Serial No. 267,400. of March 16, 1888, the same or substantially the same process is described for the treatment of the materials as in this application; but the invention is not claimed herein in the same manner.

Having thus described the nature and objects of my invention, what I claim as new, and desire to secure by Letters Patent, is-

l. The method of producing a porous crystallized metal lead plate or other structure, which consists in subjecting the salts of lead,

zinc, and cadmium to fusion, then casting the fused mass in a mold and allowing,r it to crystallize therein, and then reducing the structure to a metallic state, substantially as and for the purposes set forth.

2. The method of producing a porous crystallized metal structure, which consists `in fusing together the chlorides ot' lead, zinc, and cadmium, then casting the mass in a mold and allowing it to cool and crystallize therein, and then reducing electrolytically the structure to a metallic state. substantially as and for the purposes set forth.

In witness whereof I- have hereunto set my hand in the presence of two subscribing Witnesses.

CLEMENT PAYEN. Witnesses:

J. WALTER DoUGLAss, HERMANN HORMANN. 

